Fungicidal substituted triazoles

ABSTRACT

Fungicidal trazoles of the formula ##STR1## in which Ar stands for optionally substituted aryl, 
     A stands for the groups ##STR2## and X stands for the groups ##STR3## wherein R 1  stands for hydrogen or alkyl, 
     R 2  stands for hydrogen or alkyl, 
     R 3  stands for hydrogen, alkyl, alkenyl, alkanoyl, for optionally substituted cycloalkyl or for in each case optionally substituted aralkyl or aroyl, 
     R 4  stands for hydrogen, alkyl, for optionally substituted cycloalkyl or for in each case optionally substituted aralkyl or aryl and 
     R 5  and R 6  independently of one another stand for alkyl or for optionally substituted aralkyl or together stand for an optionally substituted doubly-linked alkylene radical, 
     and addition products thereof with acids and metal salts.

The invention relates to new substituted triazoles, several processesfor their preparation and their use as fungicides.

It has already been disclosed that certain substituted triazoles possessa fungicidal activity (cf. DE-OS (German Published Specification) No.2,431,407). Thus, for example1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-ol and1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-one can be used forcombating fungi. However, the activity of these substances is notcompletely satisfactory in all fields of application, in particular atlower application rates and when low concentrations are applied.

New substituted triazoles of the formula ##STR4## in which

Ar stands for optionally substituted aryl,

A stands for the groups ##STR5## and X stands for the groups ##STR6##wherein

R¹ stands for hydrogen or alkyl,

R² stands for hydrogen or alkyl,

R³ stands for hydrogen, alkyl, alkenyl, alkanoyl, for optionallysubstituted cycloalkyl or for in each case optionally substitutedaralkyl or aroyl,

R⁴ stands for hydrogen, alkyl, for optionally substituted cycloalkyl orfor in each case optionally substituted aralkyl or aryl and

R⁵ and R⁶ independently of one another stand for alkyl or for optionallysubstituted aralkyl or together stand for an optionally substituteddoubly-linked alkylene radical,

and their acid addition salts and metal salt complexes have been found.

The compounds of the formula (I) contain at least one asymmetricallysubstituted carbon atom. Thus, they can be present in the form ofoptically active compounds. In addition, those compounds in which Astands for a --CH═CR¹ -- group can be present in the form of geometricalisomers. The present invention relates both to the pure isomers and alsoisomer mixtures.

Furthermore, it has been found that the new substituted triazoles of theformula (I) and their acid addition salts and metal salt complexes canbe prepared by a plurality of processes.

Thus,

(a) substituted triazoles of the formula ##STR7## in which

Ar and R¹ have the abovementioned meaning, are obtained when aromaticaldehydes of the formula ##STR8## in which

Ar has the abovementioned meaning are reacted with triazolylketones ofthe formula ##STR9## in which

R¹ has the abovementioned meaning if appropriate in the presence of adiluent and if appropriate in the presence of a reaction auxiliary; (b)substituted triazoles of the formula ##STR10## in which

X¹ stands for one of the groups ##STR11## and

Ar and R² have the abovementioned meaning, are obtained when substitutedtriazoles of the formula ##STR12## in which

Ar and R¹ have the abovementioned meaning, are hydrogenated withhydrogen in the presence of a hydrogenation catalyst and in the presenceof a diluent;

(c) substituted triazoles of the formula ##STR13## in which

Ar and R¹ have the abovementioned meaning, are obtained when substitutedtriazoles of the formula ##STR14## in which

Ar and R¹ have the abovementioned meaning, are reduced with complexhydrides in the presence of a diluent;

(d) substituted triazoles of the formula ##STR15## in which

R⁷ stands for alkyl, alkenyl, alkanoyl, for optionally substitutedcycloalkyl or for in each case optionally substituted aralkyl or aroyl,and Ar and A have the abovementioned meaning, are obtained whensubstituted triazoles of the formula ##STR16## in which

Ar and A have the abovementioned meaning, are reacted with compounds ofthe formula

    R.sup.7 --E                                                (IV)

in which

R⁷ has the abovementioned meaning, and

E stands for an electron-withdrawing leaving group, if appropriate inthe presence of a diluent and if appropriate in the presence of areaction auxiliary;

(e) substituted triazoles of the formula ##STR17## in which

Ar and A have the abovementioned meaning are obtained when substitutedtriazoles of the formula ##STR18## in which

Ar and A have the abovementioned meaning are reacted with an oxidizingagent if appropriate in the presence of a diluent;

(f) substituted triazoles of the formula ##STR19## in which

Ar, A and R⁴ have the abovementioned meaning, are obtained whensubstituted triazoles of the formula ##STR20## in which

Ar and A have the abovementioned meaning are reacted with hydroxylaminederivatives of the formula

    H.sub.2 N--O--R.sup.4                                      (V)

in which

R⁴ has the abovementioned meaning, or with their acid addition salts ifappropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary;

(g) substituted triazoles of the formula ##STR21## in which

Ar and A have the abovementioned meaning, and

R⁸ stands for alkyl, for optionally substituted cycloalkyl or foroptionally substituted aralkyl are obtained when substituted triazolesof the formula ##STR22## in which

Ar and A have the abovementioned meaning, are reacted with compounds ofthe formula

    R.sup.8 --E.sup.1                                          (VI)

in which

R⁸ has the abovementioned meaning, and

E¹ stands for an electron-withdrawing leaving group, if appropriate inthe presence of a diluent and if appropriate in the presence of areaction auxiliary;

(h) substituted triazoles of the formula ##STR23## in which

Ar, A, R⁵ and R⁶ have the abovementioned meaning, are obtained whensubstituted triazoles of the formula ##STR24## in which

Ar and A have the abovementioned meaning, are reacted either

(α) with alcohols of the formulae

    R.sup.5 --OH(VII) or R.sup.6 --OH                          (VIII)

in which

R⁵ and R⁶ each stand for alkyl or for optionally substituted aralkyl, or

(β) with diols of the formula ##STR25## in which

Y stands for optionally substituted alkylene, if appropriate in thepresence of a diluent and if appropriate in the presence of a reactionauxiliary, and when, if desired, an acid or a metal salt is subjected toan addition reaction with the resulting substituted triazoles of theformula (I).

Finally, it has been found that the new substituted triazoles of theformula (I) and their acid addition salts and metal salt complexespossess a good fungicidal activity.

Surprisingly, the substances according to the invention show aconsiderably better fungicidal activity than1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan1-ol and1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-one, which arechemically similar compounds of a similar type of action known from theprior art.

Formula (I) provides a general definition of the substituted triazolesaccording to the invention. Preferred compounds of the formula (I) arethose in which

Ar stands for aryl which has 6 to 10 carbon atoms and which can bemonosubstituted or polysubstituted by identical or differentsubstituents from the series comprising halogen, cyano, nitro, in eachcase straight-chain or branched alkyl, alkoxy and alkylthio, each having1 to 4 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy and halogenoalkylthio, each having 1 to 4carbon atoms and 1 to 9 identical or different halogen atoms, in eachcase straight-chain or branched alkoxycarbonyl and alkoximinoalkyl, eachhaving 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atomsin the alkyl moiety, phenyl which is optionally monosubstituted orpolysubstituted by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 4carbon atoms, phenoxy which is optionally monosubstituted orpolysubstituted by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 4carbon atoms and/or by benzyloxy which is optionally monosubstituted orpolysubstituted by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 4carbon atoms,

A stands for the group ##STR26## and

X stands for the groups ##STR27## where

R¹ stands for hydrogen or for straight-chain or branched alkyl having 1to 4 carbon atoms,

R² stands for hydrogen or straight-chain or branched alkyl having 1 to 4carbon atoms,

R³ stands for hydrogen, for in each case straight-chain or branchedalkyl having 1 to 8 carbon atoms, alkenyl having 3 to 8 carbon atoms oralkanoyl having 1 to 6 carbon atoms in the alkane moiety, furthermorestands for cycloalkyl which has 3 to 7 carbon atoms and which can bemonosubstituted or polysubstituted by identical or differentsubstituents from the series comprising halogen, straight-chain orbranched alkyl having 1 to 4 carbon atoms and/or straight-chain orbranched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identicalor different halogen atoms, or stands for aralkyl having 6 to 10 carbonatoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of the radicals tobe monosubstituted or polysubstituted in the aryl moiety by identical ordifferent substituents from the series comprising halogen, cyano, nitro,in each case straight-chain or branched alkyl, alkoxy or alkylthio, eachhaving 1 to 4 carbon atoms and/or in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy or halogenoalkylthio, each having1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, orstands for aroyl having 6 to 10 carbon atoms in the aryl moiety, itbeing possible for each of these aryl radicals to be monosubstituted orpolysubstituted by identical or different substituents from the seriescomprising halogen, cyano, nitro, in each case straight-chain orbranched alkyl, alkoxy or alkylthio, each having 1 to 4 carbon atomsand/or in each case straight-chain or branched halogenoalkyl,halogenoalkoxy or halogenoalkylthio, each having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms, R⁴ stands for hydrogen,straight-chain or branched alkyl having 1 to 6 carbon atoms or standsfor cycloalkyl having 3 to 7 carbon atoms, it being possible for each ofthe cycloalkyl radicals to be monosubstituted or polysubstituted byidentical or different substituents from the series comprising halogen,straight-chain or branched alkyl having 1 to 4 carbon atoms and/orstraight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms, or stands for aralkylhaving 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atomsin the straight-chain or branched alkyl moiety, it being possible foreach of the alkyl radicals to be monosubstituted or polysubstituted byidentical or different substituents from the series comprising halogen,cyano, nitro, in each case straight-chain or branched alkyl, alkoxy oralkylthio, each having 1 to 4 carbon atoms, in each case straight-chainor branched halogenoalkyl, halogenoalkoxy and/or halogenoalkylthio, eachhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, or stands for aryl having 6 to 10 carbon atoms, it being possiblefor each of the aryl radicals to be monosubstituted or polysubstitutedby identical or different substituents from the series comprisinghalogen, cyano, nitro, in each case straight-chain or branched alkyl,alkoxy or alkylthio, each having 1 to 4 carbon atoms, in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy and/orhalogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 9 identicalor different halogen atoms and R⁵ and R⁶ independently of one anotherstand for alkyl having 1 to 6 carbon atoms or aralkyl having 6 to 10carbon atoms in the aryl moiety and 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety, it being possible for each ofthe aryl radicals to be monosubstituted or polysubstituted by identicalor different substituents from the series comprising halogen, cyano,nitro, in each case straight-chain or branched alkyl, alkoxy oralkylthio, each having 1 to 4 carbon atoms, in each case straight-chainor branched halogenoalkyl, halogenoalkoxy and/or halogenoalkylthio, eachhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, or

R⁵ and R⁶ together stand for an alkylene radical having 2 to 4 carbonatoms, it being possible for the alkylene radical to be monosubstitutedor polysubstituted by identical or different substituents from theseries comprising straight-chain or branched alkyl having 1 to 4 carbonatoms, straight-chain or branched halogenoalkyl having 1 to 4 carbonatoms and 1 to 9 identical or different halogen atoms, alkoxyalkylhaving 1 to 4 carbon atoms in the alkyl moiety and 1 to 4 carbon atomsin the alkoxy moiety and/or aralkyloxyalkyl having 6 to 10 carbon atomsin the aryl moiety and 1 to 4 carbon atoms in the straight-chain orbranched alkyloxy moiety and also 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety, it being possible for the arylradical to be monosubstituted or polysubstituted by identical ordifferent substituents from the series comprising halogen and/or alkylhaving 1 to 4 carbon atoms.

Particularly preferred compounds of the formula (I) are those in which

Ar stands for phenyl which can be monosubstituted, disubstituted ortrisubstituted by identical or different substituents from the seriescomprising fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, difluoromethyl, fluorochloromethyl,difluorochloromethyl, trifluoromethoxy, difluoromethoxy,fluorochloromethoxy, difluorochloromethoxy, trifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl,methoximinoethyl, ethoximinoethyl, phenyl which is optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the series comprising fluorine, chlorine,bromine, methyl and/or ethyl, phenoxy which is optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the series comprising fluorine, chlorine,bromine, methyl and/or ethyl, and/or benzyloxy which is optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the series comprising fluorine, chlorine,bromine, methyl and/or ethyl,

A stands for the groups ##STR28## and

X stands for the groups ##STR29## where

R¹ stands for hydrogen, methyl, ethyl, n- or i-propyl and also n-, i-,s- or t-butyl,

R² stands for hydrogen, methyl, ethyl, n- or i-propyl and also n-, i-,s- or t-butyl,

R³ stands for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, for allyl, for straight-chain or branched butenyl, for formyl,acetyl or propionyl, furthermore stands for cyclopropyl, cyclopentyl orcyclohexyl, each of which is optionally monosubstituted, disubstitutedor trisubstituted by identical or different substituents from the seriescomprising fluorine, chlorine, bromine, methyl, ethyl and/ortrifluoromethyl, and furthermore stands for benzyl, phenethyl orbenzoyl, it being possible for each of the three abovementioned radicalsto be monosubstituted, disubstituted or trisubstituted in the phenylmoiety by identical or different substituents from the series comprisingfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, trifluoromethoxy and/ortrifluoromethylthio, R⁴ stands for hydrogen, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, furthermore stands for cyclopropyl,cyclopentyl or cyclohexyl, each of which is optionally monosubstituted,disubstituted or trisubstituted by identical or different substituentsfrom the series comprising fluorine, chlorine, bromine, methyl, ethyland/or trifluoromethyl, and furthermore stands for benzyl, phenethyl orphenyl, it being possible for each of the three abovementioned radicalsto be monosubstituted, disubstituted or trisubstituted in the phenylmoiety by identical or different substituents from the series comprisingfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, trifluoromethoxy and/ortrifluoromethylthio, and R⁵ and R⁶ each stand for methyl, ethyl orbenzyl, it being possible for the benzyl radical to be monosubstituted,disubstituted or trisubstituted in the phenyl moiety by identical ordifferent substituents from the series comprising fluorine, chlorine,bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio, or

R⁵ and R⁶ together stand for a 1,2-ethanediyl radical which can bemonosubstituted to tetrasubstituted by identical or differentsubstituents from the series comprising methyl, ethyl, n- or i-propyl,n-butyl, chloromethyl, trifluoromethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl and/or benzyloxymethyl which is optionallymonosubstituted, disubstituted or trisubstituted in the phenyl moiety byidentical or different substituents from the series comprising fluorine,chlorine, bromine, methyl and/or ethyl.

Other preferred compounds according to the invention are additionproducts of acids and those substituted triazoles of the formula (I) inwhich the substituents Ar, A and X have the meanings which have alreadybeen preferably mentioned for these substituents.

Acids which can be subjected to the addition reaction preferably includehydrohalic acids, such as, for example, hydrochloric acid andhydrobromic acid, in particular hydrochloric acid, furthermorephosphoric acid, nitric acid, sulphuric acid, mono-, bi- andtrifunctional carboxylic acids and hydroxycarboxylic acids, such as, forexample, acetic acid, maleic acid, succinic acid, fumaric acid, tartaricacid, citric acid, salicylic acid, sorbic acid and lactic acid,sulphonic acids, such as, for example, p-toluenesulphonic acid and1,5-naphthalenedisulphonic acid, and also saccharin or thiosaccharin.

Other preferred compounds according to the invention are additionproducts of salts of metals of main groups II to IV and of subgroups Iand II and also IV to VIII of the Periodic Table of the Elements andthose substituted triazoles of the formula (I) in which the substituentsAr, A and X have the meanings which have already been preferablymentioned for these substituents.

Of these, particularly preferred salts are those of copper, zinc,manganese, magnesium, tin, iron and nickel. Suitable anions of thesesalts are those which are derived from those acids which give additionproducts tolerated by plants. Particularly preferred acids of this typeare in this context the hydrohalic acids, such as, for example,hydrochloric acid and hydrobromic acid, nitric acid and sulphuric acid.

Very particularly preferred compounds of the formula (I) are those inwhich

Ar stands for phenyl which can be monosubstituted or disubstituted byidentical or different substituents from the series comprising fluorine,chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl,difluoromethyl, fluorochloromethyl, difluorochloromethyl,trifluoromethoxy, difluoromethoxy, fluorochloromethoxy,difluorochloromethoxy, trifluoromethylthio, methoximinomethyl,ethoximinomethyl, methoximinoethyl and ethoximinoethyl, phenyl which isoptionally monosubstituted or disubstituted by chlorine, phenoxy whichis optionally monosubstituted or disubstituted by chlorine or bybenzyloxy which is optionally monosubstituted or disubstituted bychlorine,

A stands for the groups ##STR30## and

X stands for the groups ##STR31## where

R¹ stands for hydrogen or methyl,

R² stands for hydrogen or methyl,

R³ stands for hydrogen, methyl, ethyl, allyl, acetyl, propionyl, forcyclohexyl, for benzyl or benzoyl which are substituted by identical ordifferent substituents from the series comprising fluorine, chlorineand/or trifluoromethoxy,

R⁴ stands for hydrogen, methyl, ethyl, cyclohexyl, for benzyl, phenethylor phenyl which are optionally monosubstituted or disubstituted bychlorine or nitro, and

R⁵ and R⁶ each stand for methyl, ethyl or benzyl or together stand for a1,2-ethanediyl radical which is optionally substituted by methyl orchloromethyl.

The following substituted triazoles of the general formula (I) may bementioned individually in addition to the compounds mentioned in thepreparation examples:

    __________________________________________________________________________     ##STR32##                                                                    Ar          A        X                                                        __________________________________________________________________________     ##STR33##                                                                                 ##STR34##                                                                              ##STR35##                                                ##STR36##                                                                                 ##STR37##                                                                              ##STR38##                                                ##STR39##                                                                                 ##STR40##                                                                              ##STR41##                                                ##STR42##                                                                                 ##STR43##                                                                              ##STR44##                                                ##STR45##                                                                                 ##STR46##                                                                              ##STR47##                                                ##STR48##                                                                                 ##STR49##                                                                              ##STR50##                                                ##STR51##                                                                                 ##STR52##                                                                              ##STR53##                                                ##STR54##                                                                                 ##STR55##                                                                              ##STR56##                                                ##STR57##                                                                                 ##STR58##                                                                              ##STR59##                                                ##STR60##                                                                                 ##STR61##                                                                              ##STR62##                                                ##STR63##                                                                                 ##STR64##                                                                              ##STR65##                                                ##STR66##                                                                                 ##STR67##                                                                              ##STR68##                                                ##STR69##                                                                                 ##STR70##                                                                              ##STR71##                                                ##STR72##                                                                                 ##STR73##                                                                              ##STR74##                                                ##STR75##                                                                                 ##STR76##                                                                              ##STR77##                                                ##STR78##                                                                                 ##STR79##                                                                              ##STR80##                                                ##STR81##                                                                                 ##STR82##                                                                              ##STR83##                                                ##STR84##                                                                                 ##STR85##                                                                              ##STR86##                                                ##STR87##                                                                                 ##STR88##                                                                              ##STR89##                                                ##STR90##                                                                                 ##STR91##                                                                              ##STR92##                                                ##STR93##                                                                                 ##STR94##                                                                              ##STR95##                                                ##STR96##                                                                                 ##STR97##                                                                              ##STR98##                                                ##STR99##                                                                                 ##STR100##                                                                             ##STR101##                                               ##STR102##                                                                                ##STR103##                                                                             ##STR104##                                               ##STR105##                                                                                ##STR106##                                                                             ##STR107##                                               ##STR108##                                                                                ##STR109##                                                                             ##STR110##                                               ##STR111##                                                                                ##STR112##                                                                             ##STR113##                                               ##STR114##                                                                                ##STR115##                                                                             ##STR116##                                               ##STR117##                                                                                ##STR118##                                                                             ##STR119##                                               ##STR120##                                                                                ##STR121##                                                                             ##STR122##                                               ##STR123##                                                                                ##STR124##                                                                             ##STR125##                                               ##STR126##                                                                                ##STR127##                                                                             ##STR128##                                               ##STR129##                                                                                ##STR130##                                                                             ##STR131##                                               ##STR132##                                                                                ##STR133##                                                                             ##STR134##                                               ##STR135##                                                                                ##STR136##                                                                             ##STR137##                                               ##STR138##                                                                                ##STR139##                                                                             ##STR140##                                               ##STR141##                                                                                ##STR142##                                                                             ##STR143##                                               ##STR144##                                                                                ##STR145##                                                                             ##STR146##                                               ##STR147##                                                                                ##STR148##                                                                             ##STR149##                                               ##STR150##                                                                                ##STR151##                                                                             ##STR152##                                               ##STR153##                                                                                ##STR154##                                                                             ##STR155##                                               ##STR156##                                                                                ##STR157##                                                                             ##STR158##                                               ##STR159##                                                                                ##STR160##                                                                             ##STR161##                                               ##STR162##                                                                                ##STR163##                                                                             ##STR164##                                               ##STR165##                                                                                ##STR166##                                                                             ##STR167##                                               ##STR168##                                                                                ##STR169##                                                                             ##STR170##                                               ##STR171##                                                                                ##STR172##                                                                             ##STR173##                                               ##STR174##                                                                                ##STR175##                                                                             ##STR176##                                               ##STR177##                                                                                ##STR178##                                                                             ##STR179##                                               ##STR180##                                                                                ##STR181##                                                                             ##STR182##                                               ##STR183##                                                                                ##STR184##                                                                             ##STR185##                                               ##STR186##                                                                                ##STR187##                                                                             ##STR188##                                               ##STR189##                                                                                ##STR190##                                                                             ##STR191##                                               ##STR192##                                                                                ##STR193##                                                                             ##STR194##                                               ##STR195##                                                                                ##STR196##                                                                             ##STR197##                                               ##STR198##                                                                                ##STR199##                                                                             ##STR200##                                               ##STR201##                                                                                ##STR202##                                                                             ##STR203##                                               ##STR204##                                                                                ##STR205##                                                                             ##STR206##                                               ##STR207##                                                                                ##STR208##                                                                             ##STR209##                                               ##STR210##                                                                                ##STR211##                                                                             ##STR212##                                               ##STR213##                                                                                ##STR214##                                                                             ##STR215##                                               ##STR216##                                                                                ##STR217##                                                                             ##STR218##                                               ##STR219##                                                                                ##STR220##                                                                             ##STR221##                                               ##STR222##                                                                                ##STR223##                                                                             ##STR224##                                               ##STR225##                                                                                ##STR226##                                                                             ##STR227##                                               ##STR228##                                                                                ##STR229##                                                                             ##STR230##                                               ##STR231##                                                                                ##STR232##                                                                             ##STR233##                                               ##STR234##                                                                                ##STR235##                                                                             ##STR236##                                               ##STR237##                                                                                ##STR238##                                                                             ##STR239##                                               ##STR240##                                                                                ##STR241##                                                                             ##STR242##                                               ##STR243## CHCH                                                                                    ##STR244##                                               ##STR245## CH.sub.2CH.sub.2                                                                        ##STR246##                                               ##STR247## CH.sub.2CH.sub.2                                                                        ##STR248##                                               ##STR249## CH.sub.2CH.sub. 2                                                                       ##STR250##                                               ##STR251## CH.sub.2CH.sub.2                                                                        ##STR252##                                               ##STR253##                                                                                ##STR254##                                                                             ##STR255##                                               ##STR256##                                                                                ##STR257##                                                                             ##STR258##                                               ##STR259##                                                                                ##STR260##                                                                             ##STR261##                                               ##STR262##                                                                                ##STR263##                                                                             ##STR264##                                               ##STR265## CHCH                                                                                    ##STR266##                                               ##STR267## CH.sub.2CH.sub.2                                                                        ##STR268##                                               ##STR269## CH.sub.2CH.sub.2                                                                        ##STR270##                                               ##STR271## CH.sub.2CH.sub.2                                                                        ##STR272##                                               ##STR273## CH.sub.2CH.sub.2                                                                        ##STR274##                                               ##STR275##                                                                                ##STR276##                                                                             ##STR277##                                               ##STR278##                                                                                ##STR279##                                                                             ##STR280##                                               ##STR281##                                                                                ##STR282##                                                                             ##STR283##                                               ##STR284##                                                                                ##STR285##                                                                             ##STR286##                                               ##STR287## CHCH                                                                                    ##STR288##                                               ##STR289## CH.sub.2CH.sub.2                                                                        ##STR290##                                               ##STR291## CH.sub.2CH.sub.2                                                                        ##STR292##                                               ##STR293## CH.sub.2CH.sub.2                                                                        ##STR294##                                               ##STR295## CH.sub.2CH.sub.2                                                                        ##STR296##                                               ##STR297##                                                                                ##STR298##                                                                             ##STR299##                                               ##STR300##                                                                                ##STR301##                                                                             ##STR302##                                               ##STR303##                                                                                ##STR304##                                                                             ##STR305##                                              __________________________________________________________________________

If, for example, 4-chlorobenzaldehyde and3-(1,2,4-triazol-1-yl)-butan-2-one are used as starting substances, thecourse of the reaction of process (a) according to the invention may berepresented by the following equation: ##STR306##

If, for example,1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one and hydrogenare used as starting substances and Raney nickel is used as thehydrogenation catalyst, the course of process (b) according to theinvention may be represented by the following equation: ##STR307##

If, for example,1-(4-chlorophenyl}-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one is used as thestarting compound and sodium borohydride is used as the complex hydride,the course of process (c) according to the invention may be representedby the following equation: ##STR308##

If, for example,1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-ol and4-chlorobenzyl chloride are used as the starting substances, the courseof process (d) according to the invention may be represented by thefollowing equation: ##STR309##

If, for example, 1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-olis used as the starting compound and dimethyl sulphoxide as theoxidizing agent, the course of process (e) according to the inventionmay be represented by the following equation: ##STR310##

If, for example,1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one and0-(2-chlorobenzyl)hydroxylamine are used as the starting substances, thecourse of process (f) according to the invention may be represented bythe following equation: ##STR311##

If, for example,1-(4-chlorophenyl)-2-methyl-4-(1,2,4-triazol-1-yl)-pentan-3-one oximeand dimethyl sulphate are used as the starting substances, the course ofprocess (g) according to the invention may be represented by thefollowing equation: ##STR312##

If, for example,1-(2,4-dichlorophenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-one and3-chloropropane-1,2-diol are used as the starting substances, the courseof process (h) according to the invention may be represented by thefollowing equation: ##STR313##

Formula (II) provides a general definition of the aromatic aldehydesrequired as starting substances for carrying out process (a) accordingto the invention. In this formula (II), Ar preferably stands for thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for this substituent.

The aromatic aldehydes of the formula (II) are generally known compoundsof organic chemistry (cf., for example, DE-OS (German PublishedSpecification) No. 3,017,339 and J. Med. Chem. 16, 1399 [1973]).

Formula (III) provides the general definition of the triazolyl ketonesfurthermore required as starting substances for carrying out process (a)according to the invention. In this formula (III), R¹ preferably standsfor those radicals which have already been mentioned in connection withthe substances of the formula (I) according to the invention as beingpreferred for this substituent.

The triazolyl ketones of the formula (III) are known (cf. DE-OS (GermanPublished Specification) No. 2,431,407).

Formula (Ia) provides a general definition of the substituted triazolesrequired as starting substances for carrying out processes (b) and (c)according to the invention. In this formula (Ia), R¹ and Ar preferablystand for those radicals which have already been mentioned in connectionwith the description of the substances of the formula (I) according tothe invention as being preferred for these substituents.

The substituted triazoles of the formula (Ia) are compounds according tothe invention and may be prepared by process (a) according to theinvention.

Formula (Ie) provides a general definition of the substituted triazolesrequired as starting substances for carrying processes (d) and (e)according to the invention. In this formula (Ie), Ar and A preferablystand for those radicals which have already been mentioned in connectionwith the description of substances of the formula (I) according to theinvention as being preferred for these substituents.

The substituted triazoles of the formula (Ie) are compounds according tothe invention and may be prepared by processes (b) or (c) according tothe invention.

Formula (IV) provides a general definition of the compounds furthermorerequired as starting substances for carrying out process (d) accordingto the invention. In this formula (IV), R⁷ preferably stands for thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for the substituent R³, with the exceptionof the hydrogen radical.

E preferably stands for halogen, in particular for chlorine, bromine oriodine, or for another leaving group which is customary in alkylating oracylating agents, such as, for example, for an alkyl, alkoxy orarylsulphonyloxy radical or an anhydride radical.

E particularly preferably stands for chlorine, bromine, iodine,methylsulphonyloxy, p-methyl-phenylsulphonyloxy or an acetic orpropionic anhydride radical.

The compounds of the formula (IV) are generally known compounds oforganic chemistry.

Formula (If) provides a general definition of the substituted triazolesrequired as starting substances for carrying out processes (f) and (h)according to the invention. In this formula (If), Ar and A preferablystand for those radicals which have already been mentioned in connectionwith the description of the substances of the formula (I) according tothe invention as being preferred for these substituents.

The substituted triazoles of the formula (If) are compounds according tothe invention and may be prepared by processes (a), (b) or (e) accordingto the invention.

Formula (V) provides a general definition of the hydroxylaminederivatives furthermore required as starting substances for carrying outprocess (f) according to the invention. In this formula (V), R⁴preferably stands for those radicals which have already been mentionedin connection with the description of the substances of the formula (I)according to the invention as being preferred for these substituents.

The hydroxylamine derivatives of the formula (V) and their acid additionsalts, such as, for example, their hydrochlorides or hydroacetates, aregenerally known compounds of organic chemistry.

Formula (Ii) provides a general definition of the substituted triazolesrequired as starting substances for carrying out process (g) accordingto the invention. In this formula (Ii), Ar and A preferably stand forthose radicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for these substituents.

The substituted triazoles of the formula (Ii) are compounds according tothe invention and may be prepared by process (f) according to theinvention.

Formula (VI) provides a general definition of the compounds furthermorerequired as starting substances for carrying out process (g) accordingto the invention. In this formula (VI), R⁸ preferably stands for thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) as being preferred forthe substituent R⁴, with the exception of the hydrogen radical and theoptionally substituted aryl radical.

E¹ preferably stands for halogen, in particular for chlorine, bromine oriodine, or for another leaving group customary in alkylating agents,such as, for example, an alkyl, alkoxy or arylsulphonyloxy group.

E¹ particularly preferably stands for chlorine, bromine, iodine,methylsulphonyloxy or p-methylphenylsulphonyloxy.

The compounds of the formula (VI) are generally known compounds oforganic chemistry.

Formulae (VII), (VIII) and (IX) provide general definitions of thealcohols and diols furthermore required as starting substances forcarrying out process (h) according to the invention. In formulae (VII)and (VIII), R⁵ and R⁶ each preferably stand for alkyl having 1 to 6carbon atoms or aralkyl having 6 to 10 carbon atoms in the aryl moietyand 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety,it being possible for each of the aryl radicals to be monosubstituted orpolysubstituted by identical or different substituents from the seriescomprising halogen, cyano, nitro, in each case straight-chain orbranched alkyl, alkoxy or alkylthio, each having 1 to 4 carbon atoms,and in each case straight-chain or branched halogenoalkyl,halogenoalkoxy and/or halogenoalkylthio, each having 1 to 4 carbon atomsand 1 to 9 identical or different halogen atoms.

In formula (IX), Y preferably stands for an alkylene radical having 2 to4 carbon atoms, it being possible for the alkylene radical to bemonosubstituted or polysubstituted by identical or differentsubstituents from the series comprising straight-chain or branched alkylhaving 1 to 4 carbon atoms, straight-chain or branched halogenoalkylhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, alkoxyalkyl having 1 to 4 carbon atoms in the alkyl moiety and 1to 4 carbon atoms in the alkoxy moiety, and/or arylalkyloxyalkyl having6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in thestraight-chain or branched alkyloxy moiety and also 1 to 4 carbon atomsin the straight-chain or branched alkyl moiety, it being possible forthe aryl moiety to be monosubstituted or polysubstituted by identical ordifferent substituents from the series comprising halogen and/or alkylhaving 1 to 4 carbon atoms.

Particularly preferred alcohols of the formula (VII) and (VIII) arethose in which

R⁵ or R⁶ each stand for methyl, ethyl or benzyl, it being possible forthe benzyl radical to be monosubstituted, disubstituted ortrisubstituted in the phenyl moiety by substituents from the seriescomprising fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.

Other especially preferred diols of the formula (IX) are those in whichY stands for a 1,2-ethanediyl radical which can be monosubstituted totetrasubstituted by identical or different substituents from the seriescomprising methyl, ethyl, n- or i-propyl, n-butyl, chloromethyl,trifluoromethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxymethyland/or benzyloxymethyl which is optionally monosubstituted,disubstituted or trisubstituted in the phenyl moiety by identical ordifferent substituents from the series comprising fluorine, chlorine,bromine, methyl and/or ethyl.

Very particularly preferred alcohols of the formulae (VII) and (VIII)are those in which R⁵ or R⁶ each stand for methyl, ethyl or benzyl.

Finally, very particularly preferred diols of the formula (IX) are alsothose in which Y stands for a 1,2-ethane-diyl radical which isoptionally substituted by methyl or chloromethyl.

The alcohols of the formulae (VII) and (VIII) and also the diols of theformula (IX) are generally known compounds of organic chemistry.

Suitable diluents for carrying out process (a) according to theinvention are inert organic solvents. Diluents which can preferably beused are aliphatic, alicyclic and aromatic, optionally halogenatedhydrocarbons, such as, for example, benzine, benzene, toluene, xylene,chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,chloroform and carbon tetrachloride, ethers, such as diethyl ether,dioxane, tetrahydrofuran or ethylene glycol dimethyl or ethylene glycoldiethyl ether, nitriles, such as acetonitrile or propionitrile, amides,such as dimethylformamide, dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide, sulphoxides, suchas dimethyl sulphoxide, alcohols, such as methanol, ethanol or propanol,or heterocyclic bases, such as pyridine, and, if appropriate, also theirmixtures with water.

If appropriate, it is also possible for process (a) according to theinvention to be carried out in a two-phase system, such as, for example,water/toluene or water/dichloromethane, if appropriate in the presenceof a phase transfer catalyst. Examples of such catalysts which may bementioned are: tetrabutylammonium iodide, tetrabutylammonium bromide,tributyl-methylphosphonium bromide, trimethyl-C₁₃ /C₁₅ -alkylammoniumchloride, dibenzyldimethylammonium methylsulphate, dimethyl-C₁₂ /C₁₄-alkylbenzylammonium chloride, tetrabutylammonium hydroxide, 15-crown-5,18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammoniumchloride or tris-[2-(2-methoxyethoxy)-ethyl]-amine.

Process (a) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all inorganic or organic bases or acids which can customarily beused. The hydroxides, alkoxides, carbonates or hydrogen carbonates ofalkali metals, such as, for example, sodium hydroxide, sodium methoxide,sodium ethoxide, potassium t-butoxide, sodium carbonate, potassiumcarbonate or sodium hydrogen carbonate, and also amines, such as, forexample, triethylamine, N,N-dimethylaniline, pyridine, piperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU), or acids, suchas, for example, hydrochloric acid or acetic acid, and also mixtures ofacids and bases of the abovementioned type, can preferably be used.

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between -50° C. and +200°C., preferably at temperatures of between 0° C. and 150° C.

1.0 to 1.5 moles, preferably 1.0 to 1.2 moles, of triazolyl ketone ofthe formula (III) and if appropriate 0.01 to 1.0 mole, preferably 0.1 to0.5 mole, of reaction auxiliary are generally employed per mole ofaromatic aldehyde of the formula (II) for carrying out process (a)according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable hydrogenation catalysts for carrying out process (b) accordingto the invention are all customary noble metal, noble metal oxide andRaney hydrogenation catalysts. Raney nickel is particularly preferablyused as a hydrogenation catalyst.

Suitable diluents for carrying out process (b) according to theinvention are also inert organic solvents. The diluents mentioned inprocess (a) or esters, such as ethyl acetate, are preferably used.

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between 0° C. and 200° C.,preferably at temperatures of between 20° C. and 150° C.

Process (b) according to the invention is generally carried out underpressure. The process is preferably carried out under a hydrogenpressure of between 1 and 200 bar, in particular between 10 and 100 bar.

0.001 to 0.5 mole, preferably 0.01 to 0.1 mole, of hydrogenationcatalyst and also an excess of hydrogen are generally employed per moleof substituted triazole of the formula (Ia) for carrying out process (b)according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods.

Depending on the types of the substituents in the starting compounds ofthe formula (Ia) and depending on the reaction conditions (temperature,amount of catalyst, hydrogen pressure, reaction time) the initial resultis hydrogenation of the C=C double bond in the molecule and thenpossibly further hydrogenation of the C=O double bond, so that either1-aryl-4-triazolylpentan3-ones or 1-aryl-4-triazolylpentan-3-ols can beobtained as the final products (cf. also the preparation examples).

Process (c) according to the invention is carried out in the presence ofa customary complex hydride as the reducing agent. Sodium borohydride,sodium cyanoborohydride or lithium borohydride are particularlypreferably used, if appropriate in the presence of calcium chloride, italso being possible for complex calcium borohydrides to be formed in thereaction mixture.

Suitable diluents for carrying out process (c) according to theinvention are inert organic solvents. Ethers, such as diethyl ether,dioxane, tetrahydrofuran or ethylene glycol dimethyl or ethylene glycoldiethyl ether, or alcohols, such as methanol, ethanol and also n- ori-propanol, are preferably used, if appropriate also in the form of amixture with water.

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between -100° C. and +200°C., preferably at temperatures of between -50° C. and +50° C.

0.1 to 1.5 moles, preferably 0.25 to 1.0 mole, of complex hydride and ifappropriate 0.1 to 1.5 moles, preferably 0.25 to 1.0 mole, of calciumchloride are generally employed per mole of substituted triazole of theformula (Ia) for carrying out process (c) according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable diluents for carrying out process (d) according to theinvention are inert organic solvents. Aliphatic, alicyclic or aromaticoptionally halogenated hydrocarbons, such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, chloroform and carbon tetrachloride,ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl or ethylene glycol diethyl ether, ketones, such asacetone or butanone, nitriles, such as acetonitrile or propionitrile,amides, such as dimethylformamide, dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide, esters, such as ethyl acetate, or sulphoxides, such asdimethyl sulphoxide, can preferably be used.

If appropriate, process (d) according to the invention can alternativelybe carried out in a two-phase system, such as, for example,water/toluene or water/dichloromethane, if appropriate in the presenceof a phase transfer catalyst. Examples of such catalysts which may bementioned are: tetrabutylammonium iodide, tetrabutylammonium bromide,tributyl-methylphosphonium bromide, trimethyl-C₁₃ /C₁₅ -alkylammoniumchloride, dibenzyldimethylammonium methylsulphate, dimethyl-C₁₂ /C₁₄-alkyl-benzylammonium chloride, tetrabutylammonium hydroxide,15-crown-5, 18-crown-6, triethylbenzylammonium chloride andtrimethylbenzylammonium chloride.

Process (d) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all inorganic or organic bases which can customarily be used. Thehydrides, hydroxides, amides, alkoxides, carbonates or hydrogencarbonates of alkali metals, such as, for example sodium hydride, sodiumamide, sodium hydroxide, sodium methoxide, sodium ethoxide, potassiumt-butoxide, sodium carbonate or sodium hydrogen carbonate, and alsotertiary amines, such as triethylamine, N,N-dimethylaniline, pyridine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU) are preferablyused.

When carrying out the reactions of process (d) according to theinvention, it can also be advantageous to add small amounts of customaryalkylation catalysts, such as, for example, potassium iodide.

When carrying out process (d) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between -50° C. and 200°C., preferably at temperatures of between 0° C. and 100° C.

1.0 to 5.0 moles, preferably 1.0 to 1.5 moles, of a compound of theformula (IV) and if appropriate 1.0 to 3.0 moles, preferably 1.0 to 1.2moles, of reaction auxiliary are generally employed per mole ofsubstituted triazole of the formula (Ie) for carrying out process (d)according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable oxidizing agents for carrying out process (e) according to theinvention are all oxidizing agents which are customarily used inoxidation reactions of alcohols of this type. Dimethyl sulphoxide in thepresence of suitable auxiliary reagents, such as, for example, oxalylchloride in the presence of triethylamine or acetic anhydride, orsulphur trioxide in the presence of pyridine and triethylamine, orp-toluenesulphonyl chloride or sulphonic anhydrides, such asmethanesulphonic anhydride or trifluoromethanesulphonic anhydride, orcyanuric halides or chlorine or mercury acetate or silvertetrafluoroborate in the presence of triethylamine, or potassium iodidein the presence of sodium hydrogen carbonate, which bind the waterliberated during the reaction, are particularly preferably used.

Suitable diluents for carrying out process (e) according to theinvention are inert organic solvents. Aliphatic, alicyclic or aromaticoptionally halogenated hydrocarbons, such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, chloroform and carbon tetrachloride,ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl or ethylene glycol diethyl ether, ketones, such asacetone or butanone, nitriles, such as acetonitrile or propionitrile,amides, such as dimethylformamide, dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide, esters, such as ethyl acetate, or sulphoxides, such asdimethyl sulphoxide, which can be employed simultaneously as theoxidizing agent and as the diluent, can preferably be used.

When carrying out process (e) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between -80° C. and +50°C., preferably at temperatures of between -80° C. and 0° C.

1.0 to 30.0 moles, preferably 1.0 to 5.0 moles, of oxidizing agent areemployed per mole of substituted triazole of the formula (Ie) forcarrying out process (e) according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable diluents for carrying out process (f) according to theinvention are inert organic solvents. Aliphatic, alicyclic or aromatic,optionally halogenated hydrocarbons, such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, chloroform and carbon tetrachloride,ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl or ethylene glycol diethyl ether, nitriles, such asacetonitrile or propionitrile, amides, such as dimethylformamide,dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide, esters, such as ethyl acetate, orsulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol orethanol, or basic solvents, such as pyridine of triethylamine, canpreferably be used.

Process (f) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all inorganic and organic bases which can customarily be employed.The hydrides, hydroxides, alkoxides, carbonates or hydrogen carbonatesof alkali metals, such as, for example, sodium hydroxide, sodiummethoxide, sodium ethoxide, potassium t-butoxide, sodium carbonate,potassium carbonate or sodium hydrogen carbonate, and also tertiaryamines, such as, for example, triethylamine, N,N-dimethylaniline,pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU) are preferablyused. If appropriate, acid reaction auxiliaries such as, for example,p-toluenesulphonic acid, are also advantageous.

When carrying out process (f) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between -50° C. and +150°C., preferably at temperatures of between 0° C. and 50° C.

1.0 to 2.0 moles, preferably 1.0 to 1.2 moles, of hydroxylaminederivative of the formula (V) or of a corresponding acid addition salt,and if appropriate 0.01 to 20.0 moles, preferably 0.1 to 3.0 moles, ofreaction auxiliary are employed per mole of substituted triazole of theformula (If) for carrying out process (f) according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

Suitable diluents for carrying out process (g) according to theinvention are inert organic solvents. Aliphatic, alicyclic or aromatic,optionally halogenated hydrocarbons, such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, chloroform and carbon tetrachloride,ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl or ethylene glycol diethyl ether, ketones, such asacetone or butanone, nitriles, such as acetonitrile or propionitrile,amides, such as dimethylformamide, dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide, esters, such as ethyl acetate, or sulphoxides, such asdimethyl sulphoxides, can preferably be used.

If appropriate, process (g) can alternatively be carried out in atwo-phase system, such as, for example, water/toluene orwater/dichloromethane, if appropriate in the presence of a phasetransfer catalyst. Examples of such catalysts which may be mentionedare: tetrabutylammonium iodide, tetrabutylammonium bromide,tributylmethylphosphonium bromide, trimethyl-C₁₃ /C₁₅ -alkylammmoniumchloride, dibenzyl-dimethylammonium methylsulphate, dimethyl-C₁₂ /C₁₄-alkyl-benzylammonium chloride, tetrabutylammonium hydroxide,15-crown-5, 18-crown-6, triethylbenzylammonium chloride andtrimethylbenzylammonium chloride.

Process (g) according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all the inorganic and organic bases which can customarily be used.The hydrides, hydroxides, alkoxides, carbonates or hydrogen carbonatesof alkali metals, such as, for example, sodium hydride, sodiumhydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide,sodium carbonate, potassium carbonate or sodium hydrogen carbonate, andalso tertiary amines, such as, for example, triethylamine,N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU) are preferably used.

When carrying out process (g) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures of between 0° C. and 120° C.,preferably at temperatures of between 20° C. and 100° C.

1.0 to 10.0 moles, preferably 1.0 to 3.0 moles, of a compound of theformula (VI) and if appropriate 1.0 to 5.0 moles, preferably 1.0 to 3.0moles, of reaction auxiliary are generally employed per mole ofsubstituted triazole of the formula (Ii) for carrying out process (g)according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods.

Suitable diluents for carrying out process (h) according to theinvention are inert organic solvents. Aliphatic, alicyclic or aromatic,optionally halogenated hydrocarbons, such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, chloroform and carbon tetrachloride, orethers, such as diethyl ether, dioxane, tetrahydrofuran or ethyleneglycol dimethyl or ethylene glycol diethyl ether, can preferably beused.

Process (h) is preferably carried out in the presence of a suitablereaction auxiliary. Suitable reaction auxiliaries are all inorganic ororganic acids which can customarily be used, or other customarycatalysts. Diluted aqueous or concentrated mineral acids, such ashydrochloric acid, sulphuric acid or phosphoric acid, or organicsulphonic acids, such as methanesulphonic acid or p-toluenesulphonicacid, are particularly preferably used.

When carrying out process (h) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures from between 0° C. and 200°C., preferably at temperatures of between 20° C. and 150° C.

1.0 to 30.0 moles, preferably 1.0 to 5.0 moles, of alcohol or diol ofthe formulae (VII), (VIII) or (IX), and if appropriate 0.01 to 2.0moles, preferably 0.1 to 1.0 mole, of reaction auxiliary are employedper mole of substituted triazole of the formula (If) for carrying outprocess (h) according to the invention.

The reaction is carried out, and the reaction products are worked up andisolated by generally customary methods (cf. also the preparationexamples).

The acid addition salts of the compounds of the formula (I) can beprepared in a simple manner by customary salt formation methods, suchas, for example, by dissolving a compound of the formula (I) in asuitable inert solvent and adding the acid, such as, for example,hydrochloric acid, and they can be isolated in a known manner, forexample by filtration, and, if appropriate, purified by washing with aninert organic solvent.

The metal salt complexes of compounds of the formula (I) can be obtainedin a simple manner by customary processes, thus, for example, bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to the compound of the formula (I). Metal salt complexescan be isolated in a known manner, for example by filtration, and, ifappropriate, purified by recrystallization.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice as fungicides andbactericides for combating undesired microorganisms.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation: Pythium species, such as, for example, Pythium ultimum;Phytophthora species, such as, for example, Phytophthora infestans;Pseudoperonospora species, such as, for example, Pseudoperonspora-humulior Pseudoperonospora cubensis; Plasmopara species, such as, for example,Plasmopara viticola; Peronospora species, such as, for example,Peronospora pisi or P. brassicae; Erysiphe species, such as, forexample, Erysiphe graminis; Sphaerotheca species, such as, for example,Erysiphe graminis; Sphaerotheca species, such as for example,Sphaerotheca fuliginea; Podosphaera species, such as, for example,Podosphaera leucotricha; Venturia species, such as, for example,Venturia inaequalis; Pyrenophora species, such as, for example,Pyrenophora teres or P. graminea (conidia form: Drechslera, syn:Helminthosporium); Cochliobolus species, such as, for example,Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as, for example, Uromyces appendiculatus;Puccinia species, such as, for example, Puccinia recondita; Tilletiaspecies, such as, for example, Tilletia caries; Ustilago species, suchas, for example, Ustilago nuda or Ustilago avenae; Pellicularia species,such as, for example, Pellicularia sasakii; Pyricularia species, suchas, for example, Pyriculria oryzae; Fusarium species, such as, forexample, Fusarium culmorum; Potrytis species, such as, for example,Botrytis cinerea; Septoria species, such as, for example, Septorianodorum; Leptosphaeria species, such as, for example, Leptosphaerianodorum; Cercospora species, such as, for example, Cercospora canescens;Alternaria species, such as, for example, Alternaria brassicae andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

Here, the active compounds according to the invention can be employedwith particularly good success for combating cereal diseases, such as,for example, against the causative organism of leaf spot of wheat(Leptosphaeria nodorum) or against the causative organism of net blotchof barley (Pyrenophora teres) or against the causative organism of footrot disease of wheat (Cochliobolus sativus) or against the causativeorganism of powdery mildew of cereals (Erysiphe graminis) or against thecausative organism of snow mould of cereals (Fusarium nivale) or againstthe causative organism of column rot of cereals (Fusarium culmorum), andalso for combating diseases in fruit growing and vegetable growing, suchas, for example, against the causative organism of apple scab (Venturiainaequalis) or against the causative organism of powdery mildew ofcucurbits (Sphaerotheca fuliginea), or for combating rice diseases, suchas, for example, against the causative organism of rice blot disease(Pyricularia oryzae).

In addition, the active compounds according to the invention alsopossess a plant growth-regulating activity.

Finally, the active compounds according to the invention can be employedin the protection of materials for protecting industrial materialsagainst contamination by microorganisms. Technical materials in thiscontext are taken to mean non-living materials which have been preparedfor use in industry. For example, industrial materials which are to beprotected against change or destruction by microorganisms, are glues,sizes, paper, board, textiles, leather, wood, paints, articles made ofplastic, cooling lubricants and other materials which can becontaminated or destroyed by microorganisms. Within the scope of thematerials to be protected, parts of production plants which can beimpaired by multiplication of microorganisms, may also be mentioned, forexample cooling water circuits. Industrial materials which may bementioned in the scope of the present invention preferably are glues,sizes, paper and board, leather, wood, paints, cooling lubricants andcooling circuits, wood being particularly preferred.

Microorganisms which can cause a degradation or a change in theindustrial materials which may be mentioned are, for example, bacteria,fungi, yeasts, algae and slime organisms. The active substancesaccording to the invention preferably act against fungi, in particularmoulds, fungi which discolour and destroy wood (Basidiomycetes), andagainst slime organisms and algae.

Examples of microorganisms of the genera below which may be mentionedare:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puteana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, and also as ULV cold mist and warm mistformulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders,dusting agents and granules. They are used in the customary manner, forexample by watering, spraying, atomizing, scattering, dusting, foaming,brushing on and the like. It is furthermore possible to apply the activecompounds by the ultra-low volume method or to inject the activecompound formulation or the active compound itself into the soil. Theseeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

The examples below illustrate the preparation and the use of the activecompounds according to the invention.

PREPARATION EXAMPLES EXAMPLE 1 ##STR314##

3.8 ml (0.044 mol) of piperidine and 9.8 ml (0.171 mol) of acetic acidare added to 123.4 g (0.878 mol) of 4-chlorobenzaldehyde and 122.6 g(0.881 mol) of 3-(1,2,4-triazol-1-yl)-butan-2-one in 430 ml ofchloroform, and the mixture is refluxed over a water separator for 26hours. For working up, the cooled reaction mixture is washed insuccession with 500 ml of water, 200 ml of 40 per cent strength aqueoussodium hydrogen sulphite solution and again with 500 ml of water. Theorganic phase is dried over sodium sulphate and evaporated under reducedpressure, the residue is taken up in 200 ml of hot ethyl acetate, andthe desired product is precipitated by adding 400 ml of petroleum ether.

Following filtering off with suction and drying, 117 g (51% of theory)of 1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one of meltingpoint 115° C.-116° C. are obtained.

EXAMPLE 2 ##STR315##

5 g of Raney nickel are added to a solution of 35 g (0.14 mol) of1-(4-chlorophenyl)-4-(1,2,4-triazol1-yl)-pent-1-en-3-one in 180 ml ofmethanol, and the mixture is then hydrogenated at 60° C. to 70° C. and ahydrogen pressure of 90 to 100 bar for 2 hours, with stirring. Forworking up, the reaction mixture is filtered, the filtrate isevaporated, and the residue is recrystallized twice from diisopropylether.

24.9 g (71% of theory) of1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-one of melting point77° C.-78° C. are obtained.

EXAMPLE 3 ##STR316##

40 g of Raney nickel are added to a solution of 250 g (0.8 mol) of1-(4-trifluoromethoxyphenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one in1,500 ml of methanol, and the mixture is then hydrogenated at 90° C. to110° C. and a hydrogen pressure of 90 to 100 bar for 6.5 hours, withstirring. For working up, the reaction mixture is filtered, the filtrateis evaporated, and the residue is crystallized by stirring withdiisopropyl ether.

148 g (59% of theory) of1-(4-trifluoromethoxy-phenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-ol ofmelting point 69° C. are obtained.

EXAMPLE 4 ##STR317##

A solution of 1.26 g (0.0333 mol) of sodium borohydride in 15 ml ofwater is added dropwise, at -5° C. to 0° C., in the course of 30 minutesand with stirring to a suspension of 12.4 g (0.0474 mol) of1-(4-chlorophenyl)4-(1,2,4-triazol-1-yl)-pent-1-en-3-one and 3.53 g(0.0318 mol) of anhydrous calcium chloride in 100 ml of isopropanol,and, when the addition is complete, the mixture is stirred at roomtemperature for 2 hours. For working up, the reaction mixture isevaporated under reduced pressure and the residue remaining is added toa mixture of 150 ml of water and 10 ml of acetic acid. The mixture isextracted several times, using 50-ml portions of dichloromethane. Thecombined organic phases are washed with water, dried over sodiumsulphate and evaporated under reduced pressure, and the residue isrecrystallized from 30 ml of acetonitrile.

8.9 g (72% of theory) of1-(4-chlorophenyl)-4(1,2,4-triazol-1-yl)-pent-1-en-3-ol of melting point117° C.-118° C. are obtained.

EXAMPLE 5 ##STR318##

0.2 g (0.0012 mol) of potassium iodide is added to a suspension of 0.36g (0.012 mol) of 80 percent strength sodium hydride (in paraffin) in 20ml of absolute dimethoxyethane, and a solution of 2.6 g (0.010 mol) of1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-ol in 10 ml ofdimethoxyethane is then added dropwise, at 0° C. and with stirring. Whenthe evolution of gas has ceased, 1.6 g (0.010 mol) of 4-chlorobenzylchloride in 5 ml of dimethoxyethane are then added, and the mixture isstirred for 4 hours at room temperature and then for 20 hours at 40° C.10 ml of isopropanol are added to the cooled reaction mixture, themixture is then poured into ice water and extracted three times withdichloromethane, the organic phase is dried over sodium sulphate andconcentrated under reduced pressure, and the residue is crystallized bytreatment with a mixture of diethyl ether/n-hexane/ethanol=(5:3:1).

0.6 g (16% of theory) of1-(4-chlorophenyl)-3-(4-chlorobenzyloxy)-4-(1,2,4-triazol-1-yl)-pent-1-eneof melting point 91° C. are obtained.

EXAMPLE 6 ##STR319##

9.4 g (0.12 mol) of dimethyl sulphoxide in 10 ml of dichloromethane areadded dropwise, at -50° C. and in the course of 10 minutes to a solutionof 7.0 g (0.055 mol) of oxalyl chloride in 25 ml of absolutedichloromethane. A suspension of 15.8 g (0.05 mol) of1-(4-trifluoromethoxyphenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-ol in 25 mlof dichloromethane is then added to the mixture, likewise at -50° C.,the mixture is stirred at -50° C. for 20 minutes, 25.3 g (0.25 mol) oftriethylamine are then added, and the mixture is stirred at -50° C. fora further 10 minutes. For working up, the temperature of the reactionmixture is allowed to rise to 0° C., 20 ml of water are added, and theorganic phase is separated off. The organic phase is dried overmagnesium sulphate, and the solvent is removed under reduced pressure(0.05 mbar/50° C. ).

15 g (96% of theory) of1-(4-trifluoromethoxyphenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-one ofmelting point 58° C. are obtained.

EXAMPLE 7 ##STR320##

3.17 g (0.0379 mol) of 0-methylhydroxylamine hydrochloride are added to10.0 g (0.0379 mol) of1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pentan-3-one in 75 ml of drypyridine. The reaction mixture is stirred for 20 hours at roomtemperature and then evaporated under reduced pressure, the residue istaken up in dichloromethane and washed with water, the organic phase isdried over sodium sulphate and evaporated, again under reduced pressure,and the residue is chromatographed on silica gel (eluent: ethylacetate).

7.2 g (65% of theory) of1-(4-chlorophenyl)-3-methoximino-4-(1,2,4-triazol-1-yl)-pentane areobtained as an oil of refractive index n_(D) ²⁰ 1.5448.

EXAMPLE 8 ##STR321## 3.2 g (0.02 mol) of0-(2-chlorobenzyl)-hydroxylamine and 5.2 g (0.02 mol) of1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one are refluxedfor 18 hours over a water separator, together with 2.0 g (0.012 mol) ofp-toluenesulphonic acid in 160 ml of toluene. The salt which hasprecipitated in the cooled reaction mixture is filtered off and brieflystirred with saturated aqueous sodium hydrogen carbonate solution, themixture is filtered, and the residue is triturated with diethyl ether.

5.7 g (50% of theory) of1-(4-chlorophenyl)-3(2-chlorobenzyloximino)-4-(1,2,4-triazol-1-yl)-pent-1-enep-toluenesulphonate of melting point 167° C. are obtained.

EXAMPLE 9 ##STR322##

5.5 g (0.0096 mol) of1-(4-chlorophenyl)-3-(2-chlorobenzyloximino)-4-(1,2,4-triazol-1-yl)-pent-1-enep-toluenesulphonate are stirred together with 2.0 g (0.02 mol) oftriethylamine in 20 ml of dichloromethane at room temperature for 10minutes. The reaction mixture is then washed with 10 ml of water, theorganic phase is dried over sodium sulphate, and the solvent is removedunder reduced pressure.

3.6 g (99% of theory) of1-(4-chlorophenyl)-3-(2-chlorobenzyloximino)-4-(1,2,4-triazol-1-yl)-pent-1-eneare obtained as an oil of refractive index n_(D) ²⁰ 1.6101.

EXAMPLE 10 ##STR323##

3.5 g (0.013 mol) of1-(4-chlorophenyl)-4-(1,2,4-triazol-1-yl)-pent-1-en-3-one and 1.77 g(0.016 mol) of 3-chloropropane-1,2-diol are refluxed for 82 hours with0.1 ml of methanesulphonic acid in 100 ml of absolute toluene. Thereaction mixture is then washed 3 times with 100 ml portions of 0.1 Naqueous sodium hydroxide solution and then 3 times with 50 ml portionsof water. The organic phase is dried over potassium carbonate, thesolvent is distilled off, and the residue is chromatographed graphedover silica gel (eluent: ethyl acetate).

1.45 g (31% of theory) of2-[1-(1,2,4-triazol-1-yl)-ethyl]-2-[2-(4-chlorophenyl)-ethenyl]-4-chloromethyl1,3-dioxolaneare obtained as an oil of refractive index n_(D) ²⁰ =1.5591.

The substituted triazoles of the formula ##STR324## which are listed inTable 1 below are prepared in an analogous manner and following thegeneral instructions for the preparation.

                                      TABLE 1                                     __________________________________________________________________________    Example                                   Physical                            No.  Ar         A        X                properties                          __________________________________________________________________________    11                                                                                  ##STR325##                                                                              CHCH                                                                                    ##STR326##      Mp 80-82° C.                 12                                                                                  ##STR327##                                                                              CHCH                                                                                    ##STR328##      Mp 104-106° C.               13                                                                                  ##STR329##                                                                              CHCH                                                                                    ##STR330##      n.sub.D.sup.20 1.5159               14                                                                                  ##STR331##                                                                              CHCH                                                                                    ##STR332##      Mp 124-126° C.               15                                                                                  ##STR333##                                                                               ##STR334##                                                                             ##STR335##      n.sub.D.sup.20 1.5310               16                                                                                  ##STR336##                                                                               ##STR337##                                                                             ##STR338##      Mp 56-58° C.                 17                                                                                  ##STR339##                                                                               ##STR340##                                                                             ##STR341##      Mp 114-116° C.               18                                                                                  ##STR342##                                                                              CHCH                                                                                    ##STR343##      Mp 102-104° C.               19                                                                                  ##STR344##                                                                               ##STR345##                                                                             ##STR346##      n.sub.D.sup.20 1.5068               20                                                                                  ##STR347##                                                                               ##STR348##                                                                             ##STR349##      n.sub.D.sup.20 1.5770               21                                                                                  ##STR350##                                                                              CHCH                                                                                    ##STR351##      n.sub.D.sup.20 1.5400               22                                                                                  ##STR352##                                                                              CHCH                                                                                    ##STR353##      n.sub.D.sup.20 1.5408               23                                                                                  ##STR354##                                                                              CHCH                                                                                    ##STR355##      n.sub.D.sup.20 1.5543               24                                                                                  ##STR356##                                                                               ##STR357##                                                                             ##STR358##      n.sub.D.sup.20 1.5766               25                                                                                  ##STR359##                                                                               ##STR360##                                                                             ##STR361##      Mp 78-80° C.                 26                                                                                  ##STR362##                                                                              CH.sub.2CH.sub.2                                                                        ##STR363##      n.sub.D.sup.20 1.5546               27                                                                                  ##STR364##                                                                              CHCH                                                                                    ##STR365##      n.sub.D.sup.20 1,5515               28                                                                                  ##STR366##                                                                              CHCH                                                                                    ##STR367##      n.sub.D.sup.20 1.6095               29                                                                                  ##STR368##                                                                              CH.sub.2CH.sub.2                                                                        ##STR369##      n.sub.D.sup.20 1.5520               30                                                                                  ##STR370##                                                                               ##STR371##                                                                             ##STR372##      n.sub.D.sup.20 1.5720               31                                                                                  ##STR373##                                                                              CHCH                                                                                    ##STR374##      Mp 169-170° C.               32                                                                                  ##STR375##                                                                              CH.sub.2CH.sub.2                                                                        ##STR376##      n.sub.D.sup.20 1.4918               33                                                                                  ##STR377##                                                                              CHCH                                                                                    ##STR378##      n.sub.D.sup.20 1.5180               34                                                                                  ##STR379##                                                                              CHCH                                                                                    ##STR380##      Mp 96° C.                    35                                                                                  ##STR381##                                                                              CHCH                                                                                    ##STR382##      n.sub.D.sup.20 1.5180               36                                                                                  ##STR383##                                                                              CHCH                                                                                    ##STR384##      Mp 144° C.                   37                                                                                  ##STR385##                                                                              CHCH                                                                                    ##STR386##      n.sub.D.sup.20 1.5810               38                                                                                  ##STR387##                                                                               ##STR388##                                                                             ##STR389##      n.sub.D.sup.20 1.5522               39                                                                                  ##STR390##                                                                              CH.sub.2CH.sub.2                                                                        ##STR391##      n.sub.D.sup.20 1.5578               40                                                                                  ##STR392##                                                                              CH.sub.2CH.sub.2                                                                        ##STR393##      n.sub.D.sup.20 1,5492               41                                                                                  ##STR394##                                                                              CH.sub.2CH.sub.2                                                                        ##STR395##      n.sub.D.sup.22 1,5296               42                                                                                  ##STR396##                                                                              CH.sub.2CH.sub.2                                                                        ##STR397##      n.sub.D.sup.22 1.5370               43                                                                                  ##STR398##                                                                              CH.sub.2CH.sub.2                                                                        ##STR399##      n.sub.D.sup.20 1.5092               44                                                                                  ##STR400##                                                                              CH.sub.2CH.sub.2                                                                        ##STR401##      n.sub.D.sup.22 1.5110               45                                                                                  ##STR402##                                                                              CH.sub.2CH.sub.2                                                                        ##STR403##      n.sub.D.sup.23 1.5217               46                                                                                  ##STR404##                                                                              CH.sub.2CH.sub.2                                                                        ##STR405##      n.sub.D.sup.23 1,5498               47                                                                                  ##STR406##                                                                              CH.sub.2CH.sub.2                                                                        ##STR407##      n.sub.D.sup.23 1.5632               48                                                                                  ##STR408##                                                                              CH.sub.2CH.sub.2                                                                        ##STR409##      n.sub.D.sup.23 1.5529               49                                                                                  ##STR410##                                                                              CH.sub.2CH.sub.2                                                                        ##STR411##      n.sub.D.sup.23 1.5731               50                                                                                  ##STR412##                                                                              CH.sub.2CH.sub.2                                                                        ##STR413##      n.sub.D.sup.23 1.5575               51                                                                                  ##STR414##                                                                              CH.sub.2CH.sub.2                                                                        ##STR415##      Mp 124° C.                   52                                                                                  ##STR416##                                                                              CH.sub.2 CH.sub.2                                                                       ##STR417##      Mp 224° C.                    ##STR418##                                                                   53                                                                                  ##STR419##                                                                              CH.sub.2CH.sub.2                                                                        ##STR420##      Mp 110° C.                    ##STR421##                                                                   __________________________________________________________________________

Use Examples

In the following use examples, the compounds listed below have beenemployed as comparison substances: ##STR422##(1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-one ##STR423##1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-propan-1-ol (both disclosed inDE-OS (German Published Specification No. 2,431,407)

Example A

Pyrenophora teres test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants remain in an incubation cabin at 20° C.and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the substances according to the invention given inExamples 7, 19, 21, 29, 32 and 33 show a considerably better activitythan comparison substances (A) and (B).

Example B

Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the substances according to the invention given inExamples 7, 19, 20, 21, 29, 32 and 33 show a considerably betteractivity than comparison substances (A) and (B).

Example C

In order to determine the activity against fungi which are to becombated in the protection of materials, the minimum inhibitoryconcentrations (MIC) of active compounds according to the invention aredetermined.

Active compounds according to the invention are added, in concentrationsof 0.1 mg/l to 5,000 mg/l, to an agar which is prepared using brewer'swort and peptone. When the agar has solidified, it is contaminated withpure cultures of test organisms. The agar is stored at 28° C. and 60 to70% relative atmospheric humidity for 2 weeks, and the MIC isdetermined. MIC is the lowest concentration of active compound at whichno growth whatsoever by the species of microbe used takes place.

In this test, the active compounds according to the invention given inExamples 1, 7 and 12 show MIC values of between 50 and 1,000 mg/l forAspergillus niger, Chaetomium globosum and Penicillium glaucum.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. A substituted triazole of the formula ##STR424##in which Ar stands for aryl which has 6 to 10 carbon atoms and which canbe monosubstituted or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, nitro, in eachcase straight-chain or branched alkyl, alkoxy and alkylthio, each having1 to 4 carbon atoms, in each case straight-chain or branchedhalogenalkyl, halogenoalkoxy and halogenoalkyhlthio, each having 1 to 4carbon atoms and 1 to 9 identical or different halogen atoms, in eachcase straight-chain or branched alkoxycarbonyl and alkoximinoalkyl, eachhaving 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atomsin the alkyl moiety, phenyl which is optionally monosubstituted orpolysubstituted by identical or different substituents from the groupconsisting of halogen and straight-chain or branched alkyl having 1 to 4carbon atoms, phenoxy which is optionally monosubstituted orpolysubstituted by identical or different substituents from the groupconsisting of halogen and straight-chain or branched alkyl having 1 to 4carbon atoms and by benzyloxy which is optionally monosubstituted orpolysubstituted by identical or different substituents from the groupconsisting of halogen and straight-chain or branched alkyl having 1 to 4carbon atoms,A stands for the group ##STR425## R¹ stands for hydrogen orfor straight-chain or branched alkyl having 1 to 4 carbon atoms, R²stands for hydrogen or straight-chain or branched alkyl having 1 to 4carbon atoms, R⁴ stands for hydrogen, straight-chain or branched alkylhaving 1 to 6 carbon atoms or stands for cycloalkyl having 3 to 7 carbonatoms, it being possible for each of the cycloalkyl radicals to bemonosubstituted or polysubstituted by identical or differentsubstituents from the group consisting of halogen, straight-chain orbranched alkyl having 1 to 4 carbon atoms and straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms, or stands for aralkyl having 6 to 10 carbonatoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, it being possible for each of the alkylradicals to be monosubstituted or polysubstituted by identical ordifferent substituents from the group consisting of halogen, cyano,nitro, in each case straight-chain or branched alkyl, alkyloxy oralkylthio, each having 1 to 4 carbon atoms, in each case straight-chainor branched halogenoalkyl, halogenoalkoxy and halogenoalkythio, eachhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms, or stands for aryl having 6 to 10 carbon atoms, it being possiblefor each of the aryl radicals to be monosubstituted or polysubstitutedby identical or different substituents from the group consisting ofhalogen, cyano, nitro, in each case straight-chain or branched alkyl,alkoxy or alkylthio, each having 1 to 4 carbon atoms, in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy andhalogenoalkylthio, each having 1 to 4 carbon atoms and 1 to 9 identicalor different halogen atoms,or an addition product thereof with an acidor metal salt.
 2. A substituted triazole or addition product thereofaccording to claim 1,in which Ar stands for phenyl which can bemonosubstituted disubstituted or trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl,difluromethyl, fluorochloromethyl, difluorochloromethyl,trifluoromethoxy, difluromethoxy, fluorothloromethoxy,difluorochloromethoxy, trifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl,ethoximinoethyl, phenyl which is optionally monosubstituted,disubstituted or trisubstituted by identical or different substituentsfrom the group consisting of fluorine, chlorine, bromine, methyl andethyl, phenoxy which is optionally nonsubstituted, disubstituted ortrisubstituted by identical or different substituents from the grownconsisting of fluorine, chlorine, bromine, methyl and ethyl, andbenzyloxy which is optionally nonosubstituted, disubstituted ortrisubstituted by identical or different substitutents from the groupconsisting of fluorine, chlorine, bromine, ethyl and ethyl, A stands forthe groups ##STR426## R¹ stands for hydrogen methyl, ethyl, n- ori-propyl and n-, i-, s- or t-butyl, R² stands for hydrogen, methyl,ethyl, n- or i-propyl and n-, i-, s- or t-butyl and, R⁴ stands forhydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, forcyclopropyl, cyclopentyl or cyclohexyl, each of which is optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl and trifluoromethyl, or for benzyl, phenethyl orphenyl, it being possible for each of the three abovementioned radicalsto be monosubstituted, disubstituted or trisubstituted in the phenylmoiety by identical or different substituents from the group consistingof fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl trifluoromethoxy and trifluoromethylthio. 3.A substituted triazole or addition product thereof according to claim1,in which Ar stands for phenyl which can be monsubstituted ordisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, cyano, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethy, difluoromethyl, fluorochloromethyl,difluorochloromethyl, trifluoromethoxy, difluoromethoxy,fluorochloromethoxy, difluorochloromethoxy, trifluoromethylthio,methoximinomethyl, ethoximinomethyl, methoximinoethyl andethoximinoethyl, phenyl which is optionally monosubstituted ordisubstituted by chlorine, phenoxy which is optionally monosubstitutedor disubstituted by chlorine and by benzyloxy which is optionallymonosubstituted or disubstituted by chlorine, A stands for the groups##STR427## R¹ stands for hydrogen or methyl, R² stands for hydrogen ormethyl, and R⁴ stands for hydrogen, methyl, ethyl, cyclohexyl, orbenzyl, phenethyl or phenyl which are optionally nonosubstituted ordisubstitutes by chlorine or nitro.
 4. A substituted triazole oraddition product thereof according to claim 1,in which Ar stands forphenyl which can be monosubstituted or disubstituted by identical ordifferent substituents selected from the group consisting of fluorine,chlorine, methyl, trifluoromethyl, trifluoromethoxy and phenyl, A standsfor the groups ##STR428## wherein R¹ stands for hydrogen or methyl, andR² stands for hydrogen or methyl, and R⁴ stands for hydrogen, methyl,ethyl, phenyl which can be monosubstituted or disubstituted by identicalor different substituents selected from the group consisting offluorine, chlorine, methyl and trifluoromethyl, or represents benzyl orphenethyl each of which may be monosubstituted or disubstituted in thephenyl moiety by identical or different substituents selected from thegroup consisting of fluorine, chlorine, nitro and trifluoromethyl,or anaddition product thereof with an acid or metal salt.
 5. A compoundaccording to claim 1 wherein such compound is1-(4-trifluoromethoxy-phenyl)-2-methyl-3-methoximino-4-(1,2,4-triazol-1-yl)-pent-1-eneof the formula ##STR429## or an addition product thereof with an acid ormetal salt.
 6. A compound according to claim 1, wherein such compound is1-(4-trifluoromethoxy-phenyl)-3-methoximino-4-(1,2,4-triazol-1-yl)-pentaneof the formula ##STR430## or an addition product thereof with an acid ormetal salt.
 7. A fungicidal composition comprising a fungicidallyeffective amount of a compound or addition product thereof according toclaim 1 and an inert diluent.
 8. A method of combating fungi whichcomprises applying to such fungi or to a fungus habitat a fungicidallyeffective amount of a compound or addition product thereof according toclaim
 1. 9. The method according to claim 8, wherein such compoundis1-(4-trifluoromethoxy-phenyl)-2-methyl-3-methoximino-4-(1,2,4-triazol-1-yl)-pent-1-ene,or1-(4-trifluoromethoxy-phenyl)-3-methoximino-4-(1,2,4-triazol-1-yl)-pentane,oran addition product thereof with an acid or metal salt.